CN111454151A - Method for vaporizing dimethyl oxalate - Google Patents
Method for vaporizing dimethyl oxalate Download PDFInfo
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- CN111454151A CN111454151A CN202010336580.7A CN202010336580A CN111454151A CN 111454151 A CN111454151 A CN 111454151A CN 202010336580 A CN202010336580 A CN 202010336580A CN 111454151 A CN111454151 A CN 111454151A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01B—BOILING; BOILING APPARATUS ; EVAPORATION; EVAPORATION APPARATUS
- B01B1/00—Boiling; Boiling apparatus for physical or chemical purposes ; Evaporation in general
- B01B1/005—Evaporation for physical or chemical purposes; Evaporation apparatus therefor, e.g. evaporation of liquids for gas phase reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a method for vaporizing dimethyl oxalate, which comprises the following steps: step 1: the DMO material is divided into an upper feeding material and a lower feeding material; step 2: the upper feeding material directly enters the vaporization tower, and the lower feeding material is mixed with the preheated hydrogen feeding material to obtain a mixture and enters the vaporization tower; and step 3: the mixture drives the vaporized upper feeding materials to move upwards to leave the vaporization tower. The invention has the beneficial effects that: the method can realize complete vaporization of DMO, so that circulation is not needed, contact with a small amount of water carried in hydrogen is reduced, and generation of oxalic acid is reduced.
Description
Technical Field
The invention relates to a preparation method of ethylene glycol from coal, in particular to a method for vaporizing dimethyl oxalate.
Background
In the process of preparing ethylene glycol from coal, dimethyl oxalate (DMO) reacts with hydrogen to generate ethylene glycol. Dimethyl oxalate is in a liquid state and needs to be vaporized and uniformly mixed with hydrogen before entering a hydrogenation reactor. The droplets of the unvaporized dimethyl oxalate can be attached to the inner surface of the reaction tube of the hydrogenation reactor and the catalyst, on one hand, the liquid dimethyl oxalate can be polymerized to block the pore channel of the catalyst and coke at high temperature, on the other hand, the dimethyl oxalate can be hydrolyzed to generate oxalic acid when meeting water generated by hydrogenation reaction, so that the reaction tube of the hydrogenation reactor is corroded, and the service life of the reactor is shortened.
Chinese patent publication No. CN109482107A discloses a method and an apparatus for vaporizing dimethyl oxalate. The vaporization method comprises the following steps:
(1) mixing DMO fresh feeding material and DMO circulating material to form DMO feeding material, and preheating the DMO feeding material and then feeding the preheated DMO feeding material into a vaporization tower for vaporization;
(2) and the total hydrogen feeding is divided into two materials, the first hydrogen feeding does not enter the vaporization tower, the second hydrogen feeding enters from the bottom of the vaporization tower, and the vaporized DMO is taken out from the upper part of the vaporization tower and then is mixed with the first hydrogen feeding.
However, in this vaporization method, DMO circulates in the bottom of the vaporization tower, so that hydrolysis reaction with a small amount of water carried in hydrogen gas occurs to produce oxalic acid, which corrodes the vaporization tower and increases the equipment cost of the vaporization tower. Meanwhile, the method needs to add a plurality of devices such as a circulating storage tank, a hydrogenation feed mixer and the like, thereby increasing the device cost and the operation energy consumption.
Disclosure of Invention
The invention aims to provide a method for vaporizing dimethyl oxalate. The method can realize complete vaporization of DMO, so that circulation is not needed, contact with a small amount of water carried in hydrogen is reduced, and generation of oxalic acid is reduced.
The technical purpose of the invention is realized by the following technical scheme:
a method for vaporizing dimethyl oxalate comprises the following steps:
step 1: the DMO material is divided into an upper feeding material and a lower feeding material;
step 2: the upper feeding material directly enters the vaporization tower, and the lower feeding material is mixed with the preheated hydrogen feeding material to obtain a mixture and enters the vaporization tower;
and step 3: the mixture drives the vaporized upper feeding materials to move upwards to leave the vaporization tower.
The invention is further configured to: the DMO feed includes liquid methanol.
The invention is further configured to: the mass fraction of liquid methanol in the DMO feed is x, x is more than or equal to 15% and less than or equal to 35%, the mass fraction of DMO in the DMO feed is y, and y =100% -x.
The invention is further configured to: the hydrogen feed contains gaseous methanol.
The invention is further configured to: the mole fraction of gaseous methanol in the hydrogen feeding is m, m is more than or equal to 0.5% and less than or equal to 2.5%, and the mole fraction of hydrogen in the hydrogen feeding is n, n is more than or equal to 97.5% and less than or equal to 99.5%.
The invention is further configured to: the vaporization tower is provided with a lower filler, the upper feeding material enters the vaporization tower from the upper part of the lower filler, and the mixture enters the vaporization tower from the lower part of the lower filler.
The invention is further configured to: the vaporization tower is provided with an upper filler, and the mixture drives the vaporized upper filler to move upwards to pass through the upper filler and then leave the vaporization tower.
The invention is further configured to: the vaporization tower is provided with a liquid distributor for atomizing the upper feed after the upper feed enters.
The invention is further configured to: the vaporization tower is provided with a gas distributor for uniformly distributing the mixture after the mixture enters.
The invention is further configured to: the lower feed has a split flow rate of 15-30% of the DMO feed.
In conclusion, the invention has the following beneficial effects:
1. mixing part of liquid DMO with the preheated hydrogen, wherein the gas-liquid ratio is high at the moment, so that the liquid DMO can be completely vaporized, the liquid to be vaporized is reduced while the gas capable of vaporizing the liquid is increased in the vaporization tower, and the gas-liquid ratio in the vaporization tower is improved. Compared with the comparison document 1, in addition to more hydrogen for dispersing and heating the liquid DMO, the method also increases the amount of partially vaporized DMO for dispersing and heating the liquid DMO, so that complete vaporization of DMO is easily achieved, and the bottom of the vaporization tower almost has no residual liquid DMO, so that the vaporization tower is not easily blocked, the DMO utilization rate is improved, and the energy consumption is reduced;
2. the DMO is completely vaporized, so that circulation is not needed, the long-time stay of the liquid DMO in a vaporization tower and a reactor is reduced, the contact with a small amount of water carried in hydrogen is reduced, the DMO is hardly hydrolyzed to generate oxalic acid, and the damage to equipment is reduced;
3. methanol in the DMO feed can play a role in dissolving DMO, while methanol in the hydrogen feed can reduce the partial pressure of DMO, which is beneficial to better atomization of DMO. Methanol is a product after DMO hydrogenation, so that new substances cannot be generated due to the introduction of the methanol, and the influence on the dimethyl oxalate hydrogenation reaction is avoided;
4. the temperature requirements of DMO feeding and hydrogen feeding are low, the steam consumption is reduced, and the energy consumption is reduced;
5. on one hand, only the hydrogen feeding is heated, but the DMO feeding is not heated, on the other hand, the temperature requirements of the DMO feeding and the hydrogen feeding are low, so that the temperature of the mixture material leaving the vaporization tower and the upper feeding after vaporization is low, and the DMO is not easy to polymerize before entering the hydrogenation reactor, thereby reducing the adverse effect on the hydrogenation reaction.
Drawings
FIG. 1 is a flow chart of an embodiment of the present invention.
Reference numerals: 1. a DMO material; 2. feeding materials; 3. feeding materials downwards; 4. feeding hydrogen; 5. a preheater; 6. preheating materials; 7. mixing the materials; 8. a vaporization tower; 9. filling; 10. lower filling; 11. a liquid distributor; 12. a gas distributor; 13. reaction materials; 14. and (4) waste liquor.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
A method for vaporizing dimethyl oxalate comprises the following steps:
step 1: the DMO material containing 75% by mass of DMO and 25% by mass of methanol is divided into an upper feed and a lower feed, wherein the operating temperature of the DMO material is 125 ℃, the pressure is 4.0MPaG, and the lower feed accounts for 25% of the division ratio of the DMO feed;
step 2: preheating a hydrogen feed containing 98.5% of hydrogen in mole fraction, 1% of methanol in mole fraction and 0.5% of other components by a preheater to obtain a preheated material, mixing the preheated material and a lower feed material in a pipeline by a mixer, completely vaporizing DMO and methanol in the mixed lower feed material, and mixing to obtain a mixed material, wherein the operating temperature of the hydrogen feed is 140 ℃, the operating pressure is 3.5MPaG, the operating temperature of the preheated material is 185 ℃, and the operating temperature of the mixed material is 180 ℃;
and step 3: the upper feeding material enters the vaporization tower from the space between the upper filling material and the lower filling material of the vaporization tower, and is completely atomized after passing through a liquid distributor in the vaporization tower;
and 4, step 4: the mixture enters the vaporization tower from the lower part of the lower filler of the vaporization tower and is uniformly distributed after passing through a gas distributor in the vaporization tower;
and 5: after the completely atomized upper feeding material in the step 3 and the uniformly distributed mixture material in the step 4 are fully contacted on the lower filling material of the vaporization tower, the DMO and the methanol in the upper feeding material are completely vaporized under the dispersion and heating actions of the mixture material;
step 6: the mixture and the vaporized upper feeding material move upwards to leave the vaporization tower as the reaction material of the hydrogenation reactor after demisting through the upper filling material, and the operation temperature of the reaction material is 160 ℃;
and 7: no solution is generated at the bottom of the vaporization tower, and only a small amount of waste liquid is formed after continuous long-time operation and is discharged to an underground tank.
The upper filler is 1m in height and is positioned at the upper part of the vaporization tower; the lower packing had a height of 3m and was located in the lower part of the vaporization tower.
And detecting the bottom of the vaporization tower, wherein dimethyl oxalate is not detected. And detecting the components of the reaction material at the inlet of the hydrogenation reactor, wherein no polymerized dimethyl oxalate is detected in the reaction material. The pipeline in front of the hydrogenation reactor inlet and the inside of the reactor are detected, and acid corrosion is not detected.
Example 2
A method for vaporizing dimethyl oxalate comprises the following steps:
step 1: the DMO material containing 85 mass percent of DMO and 15 mass percent of methanol is divided into an upper feeding material and a lower feeding material, wherein the operating temperature of the DMO material is 150 ℃, the pressure is 5.0MPaG, and the lower feeding material accounts for 30 percent of the division ratio of the DMO feeding material;
step 2: preheating a hydrogen feed containing 99.4% of hydrogen in mole fraction, 0.5% of methanol in mole fraction and 0.1% of other components in mole fraction by a preheater to obtain a preheated material, mixing the preheated material and a lower feed material in a pipeline by a mixer, completely vaporizing DMO and methanol in the lower feed material after mixing, and mixing to obtain a mixed material, wherein the operating temperature of the hydrogen feed is 165 ℃, the operating pressure is 4.5MPaG, the operating temperature of the preheated material is 190 ℃, and the operating temperature of the mixed material is 185 ℃;
and step 3: the upper feeding material enters the vaporization tower from the space between the upper filling material and the lower filling material of the vaporization tower, and is completely atomized after passing through a liquid distributor in the vaporization tower;
and 4, step 4: the mixture enters the vaporization tower from the lower part of the lower filler of the vaporization tower and is uniformly distributed after passing through a gas distributor in the vaporization tower;
and 5: after the completely atomized upper feeding material in the step 3 and the uniformly distributed mixture material in the step 4 are fully contacted on the lower filling material of the vaporization tower, the DMO and the methanol in the upper feeding material are completely vaporized under the dispersion and heating actions of the mixture material;
step 6: the mixture and the vaporized upper feeding material move upwards to leave the vaporization tower as the reaction material of the hydrogenation reactor after demisting through the upper filling material, and the operation temperature of the reaction material is 180 ℃;
and 7: no solution is generated at the bottom of the vaporization tower, and only a small amount of waste liquid is formed after continuous long-time operation and is discharged to an underground tank.
The upper filler is 2m in height and is positioned at the upper part of the vaporization tower; the lower packing had a height of 5m and was located in the lower part of the vaporization tower.
And detecting the bottom of the vaporization tower, wherein dimethyl oxalate is not detected. And detecting the components of the reaction material at the inlet of the hydrogenation reactor, wherein no polymerized dimethyl oxalate is detected in the reaction material. The pipeline in front of the hydrogenation reactor inlet and the inside of the reactor are detected, and acid corrosion is not detected.
Example 3
A method for vaporizing dimethyl oxalate comprises the following steps:
step 1: the DMO material containing 65 mass percent of DMO and 35 mass percent of methanol is divided into an upper feeding material and a lower feeding material, wherein the operating temperature of the DMO material is 100 ℃, the pressure is 2.0MPaG, and the lower feeding material accounts for 15 percent of the division ratio of the DMO feeding material;
step 2: preheating a hydrogen feed containing 97.5% of hydrogen in mole fraction, 2.4% of methanol in mole fraction and 0.1% of other components in mole fraction by a preheater to obtain a preheated material, mixing the preheated material and a lower feed material in a pipeline by a mixer, completely vaporizing DMO and methanol in the lower feed material after mixing, and mixing to obtain a mixed material, wherein the operating temperature of the hydrogen feed is 125 ℃, the operating pressure is 2.0MPaG, the operating temperature of the preheated material is 150 ℃, and the operating temperature of the mixed material is 145 ℃;
and step 3: the upper feeding material enters the vaporization tower from the space between the upper filling material and the lower filling material of the vaporization tower, and is completely atomized after passing through a liquid distributor in the vaporization tower;
and 4, step 4: the mixture enters the vaporization tower from the lower part of the lower filler of the vaporization tower and is uniformly distributed after passing through a gas distributor in the vaporization tower;
and 5: after the completely atomized upper feeding material in the step 3 and the uniformly distributed mixture material in the step 4 are fully contacted on the lower filling material of the vaporization tower, the DMO and the methanol in the upper feeding material are completely vaporized under the dispersion and heating actions of the mixture material;
step 6: the mixture and the vaporized upper feeding material move upwards to leave the vaporization tower as the reaction material of the hydrogenation reactor after demisting through the upper filling material, and the operation temperature of the reaction material is 140 ℃;
and 7: no solution is generated at the bottom of the vaporization tower, and only a small amount of waste liquid is formed after continuous long-time operation and is discharged to an underground tank.
The upper filler is 0.1m in height and is positioned at the upper part of the vaporization tower; the lower packing had a height of 1m and was located in the lower part of the vaporization tower.
And detecting the bottom of the vaporization tower, wherein dimethyl oxalate is not detected. And detecting the components of the reaction material at the inlet of the hydrogenation reactor, wherein no polymerized dimethyl oxalate is detected in the reaction material. The pipeline in front of the hydrogenation reactor inlet and the inside of the reactor are detected, and acid corrosion is not detected.
Example 4
A method for vaporizing dimethyl oxalate comprises the following steps:
step 1: the DMO material containing 80% of DMO and 20% of methanol by mass is divided into an upper feeding material and a lower feeding material, wherein the operating temperature of the DMO material is 135 ℃, the pressure is 4.5MPaG, and the lower feeding material accounts for 27% of the division ratio of the DMO feeding material;
step 2: preheating a hydrogen feed containing 99% of hydrogen in mole fraction, 0.5% of methanol in mole fraction and 0.5% of other components by a preheater to obtain a preheated material, mixing the preheated material and a lower feed material in a pipeline by a mixer, completely vaporizing DMO and methanol in the mixed lower feed material, and mixing to obtain a mixed material, wherein the operating temperature of the hydrogen feed is 150 ℃, the operating pressure is 4.0MPaG, the operating temperature of the preheated material is 180 ℃, and the operating temperature of the mixed material is 175 ℃;
and step 3: the upper feeding material enters the vaporization tower from the space between the upper filling material and the lower filling material of the vaporization tower, and is completely atomized after passing through a liquid distributor in the vaporization tower;
and 4, step 4: the mixture enters the vaporization tower from the lower part of the lower filler of the vaporization tower and is uniformly distributed after passing through a gas distributor in the vaporization tower;
and 5: after the completely atomized upper feeding material in the step 3 and the uniformly distributed mixture material in the step 4 are fully contacted on the lower filling material of the vaporization tower, the DMO and the methanol in the upper feeding material are completely vaporized under the dispersion and heating actions of the mixture material;
step 6: the mixture and the vaporized upper feeding material move upwards to leave the vaporization tower as the reaction material of the hydrogenation reactor after demisting through the upper filling material, and the operation temperature of the reaction material is 170 ℃;
and 7: no solution is generated at the bottom of the vaporization tower, and only a small amount of waste liquid is formed after continuous long-time operation and is discharged to an underground tank.
The upper filler is 1.5m in height and is positioned at the upper part of the vaporization tower; the lower packing had a height of 4m and was located in the lower part of the vaporization column.
And detecting the bottom of the vaporization tower, wherein dimethyl oxalate is not detected. And detecting the components of the reaction material at the inlet of the hydrogenation reactor, wherein no polymerized dimethyl oxalate is detected in the reaction material. The pipeline in front of the hydrogenation reactor inlet and the inside of the reactor are detected, and acid corrosion is not detected.
Example 5
A method for vaporizing dimethyl oxalate comprises the following steps:
step 1: the DMO material containing 70% of DMO and 30% of methanol by mass is divided into an upper feeding material and a lower feeding material, wherein the operating temperature of the DMO material is 110 ℃, the pressure is 3.0MPaG, and the lower feeding material accounts for 20% of the division ratio of the DMO feeding material;
step 2: preheating a hydrogen feed containing 98% of hydrogen by mole fraction, 1.5% of methanol by mole fraction and 0.5% of other components by a preheater to obtain a preheated material, mixing the preheated material and a lower feed material in a pipeline by a mixer, completely vaporizing DMO and methanol in the mixed lower feed material, and mixing to obtain a mixed material, wherein the operating temperature of the hydrogen feed is 135 ℃, the operating pressure is 3.0MPaG, the operating temperature of the preheated material is 165 ℃, and the operating temperature of the mixed material is 160 ℃;
and step 3: the upper feeding material enters the vaporization tower from the space between the upper filling material and the lower filling material of the vaporization tower, and is completely atomized after passing through a liquid distributor in the vaporization tower;
and 4, step 4: the mixture enters the vaporization tower from the lower part of the lower filler of the vaporization tower and is uniformly distributed after passing through a gas distributor in the vaporization tower;
and 5: after the completely atomized upper feeding material in the step 3 and the uniformly distributed mixture material in the step 4 are fully contacted on the lower filling material of the vaporization tower, the DMO and the methanol in the upper feeding material are completely vaporized under the dispersion and heating actions of the mixture material;
step 6: the mixture and the vaporized upper feeding material move upwards to leave the vaporization tower as the reaction material of the hydrogenation reactor after demisting through the upper filling material, and the operation temperature of the reaction material is 150 ℃;
and 7: no solution is generated at the bottom of the vaporization tower, and only a small amount of waste liquid is formed after continuous long-time operation and is discharged to an underground tank.
The upper filler is 0.5m in height and is positioned at the upper part of the vaporization tower; the lower packing had a height of 2m and was located in the lower part of the vaporization column.
And detecting the bottom of the vaporization tower, wherein dimethyl oxalate is not detected. And detecting the components of the reaction material at the inlet of the hydrogenation reactor, wherein no polymerized dimethyl oxalate is detected in the reaction material. The pipeline in front of the hydrogenation reactor inlet and the inside of the reactor are detected, and acid corrosion is not detected.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications without inventive contribution to the present embodiment as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. A method for vaporizing dimethyl oxalate is characterized by comprising the following steps: the method comprises the following steps:
step 1: the DMO material is divided into an upper feeding material and a lower feeding material;
step 2: the upper feeding material directly enters the vaporization tower, and the lower feeding material is mixed with the preheated hydrogen feeding material to obtain a mixture and enters the vaporization tower;
and step 3: the mixture drives the vaporized upper feeding materials to move upwards to leave the vaporization tower.
2. The method for vaporizing dimethyl oxalate according to claim 1, wherein: the DMO feed includes liquid methanol.
3. The method for vaporizing dimethyl oxalate according to claim 2, wherein: the mass fraction of liquid methanol in the DMO feed is x, x is more than or equal to 15% and less than or equal to 35%, the mass fraction of DMO in the DMO feed is y, and y =100% -x.
4. The method for vaporizing dimethyl oxalate according to claim 1, wherein: the hydrogen feed contains gaseous methanol.
5. The method for vaporizing dimethyl oxalate according to claim 4, wherein: the mole fraction of gaseous methanol in the hydrogen feeding is m, m is more than or equal to 0.5% and less than or equal to 2.5%, and the mole fraction of hydrogen in the hydrogen feeding is n, n is more than or equal to 97.5% and less than or equal to 99.5%.
6. The method for vaporizing dimethyl oxalate according to claim 1, wherein: the vaporization tower is provided with a lower filler, the upper feeding material enters the vaporization tower from the upper part of the lower filler, and the mixture enters the vaporization tower from the lower part of the lower filler.
7. The method for vaporizing dimethyl oxalate according to claim 1, wherein: the vaporization tower is provided with an upper filler, and the mixture drives the vaporized upper filler to move upwards to pass through the upper filler and then leave the vaporization tower.
8. The method for vaporizing dimethyl oxalate according to claim 1, wherein: the vaporization tower is provided with a liquid distributor for atomizing the upper feed after the upper feed enters.
9. The method for vaporizing dimethyl oxalate according to claim 1, wherein: the vaporization tower is provided with a gas distributor for uniformly distributing the mixture after the mixture enters.
10. The method for vaporizing dimethyl oxalate according to claim 1, wherein: the lower feed has a split flow rate of 15-30% of the DMO feed.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060664A (en) * | 2010-12-23 | 2011-05-18 | 西南化工研究设计院 | High-efficiency and energy-saving reaction process for preparing ethylene glycol through hydrogenation of oxalate |
| CN104262152A (en) * | 2014-09-16 | 2015-01-07 | 上海华谊（集团）公司 | Production method of methyl glycolate |
| CA2896290A1 (en) * | 2014-07-03 | 2016-01-03 | China Petroleum & Chemical Corporation | Method for producing dimethyl oxalate |
| CN109482107A (en) * | 2018-11-30 | 2019-03-19 | 华东理工大学 | The gasification method and vapourizing unit of dimethyl oxalate |
| CN209917651U (en) * | 2019-03-27 | 2020-01-10 | 上海浦景化工技术股份有限公司 | Gas-liquid mixing gasifier |
-
2020
- 2020-04-26 CN CN202010336580.7A patent/CN111454151B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060664A (en) * | 2010-12-23 | 2011-05-18 | 西南化工研究设计院 | High-efficiency and energy-saving reaction process for preparing ethylene glycol through hydrogenation of oxalate |
| CA2896290A1 (en) * | 2014-07-03 | 2016-01-03 | China Petroleum & Chemical Corporation | Method for producing dimethyl oxalate |
| CN104262152A (en) * | 2014-09-16 | 2015-01-07 | 上海华谊（集团）公司 | Production method of methyl glycolate |
| CN109482107A (en) * | 2018-11-30 | 2019-03-19 | 华东理工大学 | The gasification method and vapourizing unit of dimethyl oxalate |
| CN209917651U (en) * | 2019-03-27 | 2020-01-10 | 上海浦景化工技术股份有限公司 | Gas-liquid mixing gasifier |
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